CN107863487A - A kind of lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell battery core and lithium-sulfur cell - Google Patents
A kind of lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell battery core and lithium-sulfur cell Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention relates to a kind of lithium-sulphur cell positive electrode and preparation method thereof, lithium-sulfur cell battery core and lithium-sulfur cell.Lithium-sulphur cell positive electrode includes collector and the active material layer compound with collector founding, and active material layer is (7.6 ± 5.1) by weight ratio：2：Aluminium, porous charcoal, the sulphur composition of (8 ± 0.5).Lithium-sulphur cell positive electrode provided by the invention, active material layer and collector founding are compound, aluminium in active material layer forms conducting metal network, porous charcoal is used to fill sulphur, the more existing lithium-sulphur cell positive electrode of electric conductivity and structural stability of gained lithium-sulphur cell positive electrode greatly improves, and can be effectively improved the high rate performance and cycle performance of lithium-sulfur cell.
Description
Technical field
The invention belongs to lithium-sulfur cell electrode field, and in particular to a kind of lithium-sulphur cell positive electrode and preparation method thereof, lithium
Sulphur battery battery core and lithium-sulfur cell.
Background technology
Lithium-sulfur cell is one kind of lithium ion battery, its using element sulphur as the positive electrode of battery, have it is in light weight,
The advantages that capacity is big, memory-less effect.The ratio energy of lithium-sulfur cell is far above commercial wide variety of lithium ion battery.And
And sulphur is a kind of environment-friendly element, environment is not polluted substantially；Lithium-sulfur cell is a kind of very promising lithium ion
Battery.
Lithium-sulfur cell is using lithium metal as negative material, and using liquid electrolyte, negative reaction is that lithium loses electronics during electric discharge
It is changed into lithium ion, positive pole reaction generates sulfide for sulphur and lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is
The discharge voltage provided by lithium-sulfur cell.Under applied voltage effect, the positive pole and negative reaction of lithium-sulfur cell inversely enter
OK, as charging process.
Application publication number is that CN105047856A patent discloses a kind of anode construction of lithium-sulfur cell, and it includes layer
The sulphur anode being stacked on aluminium foil and the carbon coating being arranged between sulphur anode and the carbon structure layer for being impregnated with sulphur；Sulphur anode bag
Sulphur, conductor and adhesive are included, the carbon structure layer for being impregnated with sulphur is and the polyester separation membrane to electrode separation；In anode construction
The loading capacity of sulphur is scattered in sulphur anode and is impregnated with the carbon structure layer of sulphur.
Existing lithium sulphur battery electrode, because the conductivity problems of binding agent and electrode material are difficult to quickly fill always
Electric discharge, and in battery charge and discharge process, there are expansion and the receipts of volume with the insertion and deintercalation of lithium ion in electrode material
Contracting, easily causes cracking and the peeling of electrode material and collector.Above-mentioned factor cause existing lithium-sulfur cell high rate performance and
Cycle performance needs further to be improved.
The content of the invention
It is an object of the invention to provide a kind of lithium-sulphur cell positive electrode, so as to solve multiplying power existing for existing lithium-sulfur cell
The problem of performance and poor circulation.
Second object of the present invention is the preparation method for providing above-mentioned lithium-sulphur cell positive electrode.
Third object of the present invention is to provide a kind of lithium-sulfur cell battery core.
Fourth object of the present invention is to provide the lithium-sulfur cell using above-mentioned lithium-sulfur cell battery core.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of lithium-sulphur cell positive electrode, including collector and the active material layer compound with collector founding, active material layer
It is (7.6 ± 5.1) by weight ratio：2：Aluminium, porous charcoal, the sulphur composition of (8 ± 0.5).
Lithium-sulphur cell positive electrode provided by the invention, active material layer and collector founding are compound, the aluminium in active material layer
Conducting metal network is formed, porous charcoal is used to fill sulphur, and the electric conductivity and structural stability of gained lithium-sulphur cell positive electrode are more existing
Lithium-sulphur cell positive electrode greatly improves, and can be effectively improved the high rate performance and cycle performance of lithium-sulfur cell.
The preparation method of above-mentioned lithium-sulphur cell positive electrode, comprises the following steps：
1) it is compressing after mixing aluminium powder, porous powdered carbon, obtain active material briquet；
2) after active material briquet is bonded with collector, under protective atmosphere, at 900~1100 DEG C founding 20~
40min, obtain founding compound collector and active material layer；
3) the compound collector of founding and active material are placed in the carbon disulfide saturated solution of sulphur and impregnated, separated,
Drying, cooling, are produced.
In step 1), aluminium powder, the ratio between the tap volume of porous powdered carbon are (2.8 ± 1.9)：2.
In step 2), the thickness of active material layer is 0.5mm~50mm.The collector is aluminium sheet, thickness is 0.3~
0.7mm。
In step 3), the temperature of the drying is 50~80 DEG C, and the time of drying is 2h~4h.
In step 3), repeat to impregnate, separate, dry, cooling down operation.The time of dipping is 0.5-2h.By above-mentioned
The load sulfur content of positive pole can be improved by repeating, and then improve the chemical property of positive pole.
The preparation method of the lithium-sulphur cell positive electrode of the present invention, active material layer is combined as a whole with collector, electric conductivity with
Structural stability greatly promotes, and high rate performance, the cycle performance of positive pole are guaranteed, and are more beneficial for the gram volume of active material
Play；The preparation method technique is simple, and the requirement to equipment is low, is applied suitable for large-scale industrialization promotion.
Technical scheme is used by the lithium-sulfur cell battery core of the present invention：
A kind of lithium-sulfur cell battery core, including diaphragm plate and the positive pole, the negative pole that are arranged on diaphragm plate both sides, positive pole is using upper
State lithium-sulphur cell positive electrode.
Negative pole includes collector and lithium plate, and the lithium plate is between collector and the diaphragm plate.The thickness of lithium plate is
0.5mm~50mm.Lithium plate is combined on a current collector by pressure.
Diaphragm plate is made up of polytetrafluoroethylene (PTFE) or ceramics, and the thickness of diaphragm plate is 0.1~0.4mm.Preferably, diaphragm plate
On the aperture in hole be 50nm~1000 μm.Distribution of the hole on diaphragm plate may be selected orderly or unordered.
The lithium-sulfur cell battery core of the present invention, using polar-plate-type composite construction, each pole plate can be adjusted according to battery design demand
Thickness, compare existing stacked and takeup type battery core, core strueture is simpler, and manufacturing cost is greatly lowered；It is high-strength
The use of large aperture division board is spent, not only increases the security performance of battery, and eliminates ion transport resistance, so as to enter
One step improves the high rate performance and cyclical stability of lithium-sulfur cell.
Using the lithium-sulfur cell of above-mentioned lithium-sulfur cell battery core.
The electrolyte of lithium-sulfur cell can use traditional lithium-ion battery electrolyte, and in electrolyte, LiPF may be selected in solute6、
LiBF4、LiClO4、LiAsF6、LiCF3SO3At least one of, diethyl carbonate, methyl ethyl carbonate, carbonic acid may be selected in solvent
At least one of dimethyl ester, ethylene carbonate, propene carbonate, glycol dimethyl ether；Lithium nitrate etc. can be further added to add
Add agent to improve the performance of electrolyte.
The lithium-sulfur cell of the present invention, manufacturing cost is low, and high rate performance, cycle performance and the security performance of battery obtain entirely
Face is lifted.
Brief description of the drawings
Fig. 1 is the structural representation of the lithium-sulfur cell battery core of the present invention.
Embodiment
Embodiments of the present invention are described further with reference to embodiment.
Embodiment 1
The lithium-sulfur cell battery core of the present embodiment, structural representation is as shown in figure 1, including diaphragm plate 12 and being located at barrier film 12
Positive plate 10, the negative plate 11 of both sides, positive plate 10 include plus plate current-collecting body 100 and compound with the founding of plus plate current-collecting body 100
Active material layer 101, negative plate 11 include negative current collector 110 and are incorporated in lithium plate on negative current collector 110 by pressure
111；
Plus plate current-collecting body 100 is aluminum pole plate, area 400cm2, thickness 0.5mm, active material layer 111 by aluminium,
Porous charcoal and sulphur composition, the thickness of active material layer is 3cm, area 400cm2, the preparation method of positive plate is：
1) it is 30 by tap volume ratio:After 70 aluminium powder and porous powdered carbon (Ketjen black powder) ball milling mixing, mould pressure is utilized
Type is made, obtains active material briquet；
2) active material briquet is fit together with plus plate current-collecting body, is placed in 1000 DEG C of inert gas stove and locates
30min is managed, room temperature is cooled to, obtains founding compound collector and active material layer；
3) the compound collector of founding and active material are placed in the carbon disulfide saturated solution of sulphur and impregnate 1h, point
From, then 3h is dried in 50 DEG C of air dry oven, it is cooled to room temperature；
4) repeat step 3) twice, produce positive plate.
In positive plate, aluminium, porous charcoal, the weight of sulphur ratio are 2.5：2：8.
Negative current collector 110 is aluminum pole plate, area 410cm2, thickness 0.5mm, the area of lithium plate is 405cm2,
Thickness is 0.4cm, and lithium plate and negative current collector are suppressed into fitting in a mold is integrated；
Diaphragm plate 12 is polytetrafluoroethylene (PTFE) macropore diaphragm plate, area 420cm2, thickness 0.2mm, on diaphragm plate uniformly
8000 ducts are distributed, aperture is 50 μm.
The lithium-sulfur cell of the present embodiment, the lithium-sulfur cell battery core of the present embodiment is inserted in pack case, draw both positive and negative polarity
Ear, electrolyte is injected, packs the lithium-sulfur cell that 3Ah is made.Electrolyte is LiPF6Solution, LiPF6Concentration be 1mol/L,
Solvent is that volume ratio is 1:1 diethyl carbonate, the mixture of methyl ethyl carbonate.
Embodiment 2
The lithium-sulfur cell battery core of the present embodiment, with embodiment 1, difference is structure：The thickness of plus plate current-collecting body is
0.4mm, the thickness of active material layer is 4.5cm；The preparation method of positive plate is：
1) it is 50 by tap volume ratio:After 50 aluminium powder and porous powdered carbon (Ketjen black powder) ball milling mixing, mould pressure is utilized
Type is made, obtains active material briquet；
2) active material briquet is fit together with plus plate current-collecting body, is placed in 900 DEG C of inert gas stove and handles
40min, room temperature is cooled to, obtains founding compound collector and active material layer；
3) the compound collector of founding and active material are placed in the carbon disulfide saturated solution of sulphur and impregnate h, point
From, then 4h is dried in 60 DEG C of air dry oven, it is cooled to room temperature；
4) repeat step 3) twice, produce positive plate.
In positive plate, aluminium, porous charcoal, the weight of sulphur ratio are 25：7：28.
The thickness of negative current collector is 0.4mm, and the thickness of lithium plate is 0.4cm.
The lithium-sulfur cell of the present embodiment, preparation process is the same as embodiment 1.
Embodiment 3
The lithium-sulfur cell battery core of the present embodiment, with embodiment 1, difference is structure：The thickness of plus plate current-collecting body is
0.5mm, the thickness of active material layer is 0.8cm；The preparation method of positive plate is：
1) it is 65 by tap volume ratio:After 35 aluminium powder and porous powdered carbon (Ketjen black powder) ball milling mixing, mould pressure is utilized
Type is made, obtains active material briquet；
2) active material briquet is fit together with plus plate current-collecting body, is placed in 1100 DEG C of inert gas stove and locates
20min is managed, room temperature is cooled to, obtains founding compound collector and active material layer；
3) the compound collector of founding and active material are placed in the carbon disulfide saturated solution of sulphur and impregnate h, point
From, then 2h is dried in 80 DEG C of air dry oven, it is cooled to room temperature；
4) repeat step 3) twice, produce positive plate.
In positive plate, aluminium, porous charcoal, the weight of sulphur ratio are 13：2.45：9.8.
The thickness of negative current collector is 0.5mm, and the thickness of lithium plate is 0.2cm.
The lithium-sulfur cell of the present embodiment, preparation process is the same as embodiment 1.
In other embodiments of the invention, the available any porous powdered carbon of Ketjen black powder is carried out etc. as described in Example 1
Amount is replaced, the lithium-sulfur cell that available can be suitable.
Test example
The chemical property and security performance of the lithium-sulfur cell of 1~embodiment of this test example detection embodiment 3, detection knot
Fruit is as shown in table 1.
The performance test results of the lithium-sulfur cell of the 1~embodiment of embodiment 3 of table 1
| Numbering | High rate performance | Cycle performance |
| Embodiment 1 | 80% capacity is kept under 20C | 100 circulation volume conservation rates 98% |
| Embodiment 2 | 85% capacity is kept under 20C | 100 circulation volume conservation rates 99% |
| Embodiment 3 | 93% capacity is kept under 20C | 100 circulation volume conservation rates 99% |
From the testing result of table 1, lithium-sulfur cell of the invention has good high rate performance and cycle performance, its
Reason is that the core strueture of polar-plate-type improves electric conductivity and structural stability, reduces ion transport resistance, while greatly
The combined use of hole division board, meeting high degree eliminate the potential safety hazard of short circuit band.
Claims (10)
- A kind of 1. lithium-sulphur cell positive electrode, it is characterised in that the compound active material layer including collector and with collector founding, it is living Property material layer is (7.6 ± 5.1) by weight ratio：2：Aluminium, porous charcoal, the sulphur composition of (8 ± 0.5).
- 2. a kind of preparation method of lithium-sulphur cell positive electrode as claimed in claim 1, it is characterised in that comprise the following steps：1) it is compressing after mixing aluminium powder, porous powdered carbon, obtain active material briquet；2) after active material briquet is bonded with collector, under protective atmosphere, 20~40min of founding at 900~1100 DEG C, Obtain founding compound collector and active material layer；3) the compound collector of founding and active material are placed in the carbon disulfide saturated solution of sulphur and impregnated, separated, drying, Cooling, is produced.
- 3. the preparation method of lithium-sulphur cell positive electrode as claimed in claim 2, it is characterised in that in step 2), active material layer Thickness be 0.5mm~50mm.
- 4. the preparation method of lithium-sulphur cell positive electrode as claimed in claim 2, it is characterised in that in step 3), the drying Temperature is 50~80 DEG C, and the time of drying is 2h~4h.
- 5. the preparation method of the lithium-sulphur cell positive electrode as described in claim 2 or 4, it is characterised in that in step 3), repeat Dipping, separation, drying, cooling down operation.
- 6. a kind of lithium-sulfur cell battery core, it is characterised in that including diaphragm plate and the positive pole, the negative pole that are arranged on diaphragm plate both sides, just Pole is using the lithium-sulphur cell positive electrode described in claim 1.
- 7. lithium-sulfur cell battery core as claimed in claim 6, it is characterised in that negative pole includes collector and lithium plate, the lithium plate Between collector and the diaphragm plate.
- 8. lithium-sulfur cell battery core as claimed in claim 6, it is characterised in that diaphragm plate is made up of polytetrafluoroethylene (PTFE) or ceramics, The thickness of diaphragm plate is 0.1~0.4mm.
- 9. lithium-sulfur cell battery core as claimed in claim 8, it is characterised in that the aperture in the hole on diaphragm plate is 50nm~1000 μm。
- A kind of 10. lithium-sulfur cell of the lithium-sulfur cell battery core described in usage right requirement 6.
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| CN109030389A (en) * | 2018-07-23 | 2018-12-18 | 中航锂电（洛阳）有限公司 | The measuring method of total sulfur in a kind of anode material for lithium-ion batteries |
| CN109216658A (en) * | 2018-10-10 | 2019-01-15 | 北京科技大学 | A kind of preparation method of the lithium-sulphur cell positive electrode of the additive containing nanometer aluminium powder |
| CN115535512A (en) * | 2022-11-24 | 2022-12-30 | 江苏时代新能源科技有限公司 | Method, device, equipment, system and storage medium for transmitting unit pole pieces |
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| CN107863487B (en) | 2020-07-17 |
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